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Development Status and Performance Comparisons of Environmental Barrier Coating Systems for SiCSiC Ceramic Matrix Composites

Environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft turbine engine systems, because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. This paper presents current NASA EBC-CMC development emphases including: the coating composition and processing improvements, laser high heat flux-thermal gradient thermo-mechanical fatigue - environmental testing methodology development, and property evaluations for next generation EBC-CMC systems. EBCs processed with various deposition techniques including Plasma Spray, Electron Beam - Physical Vapor Deposition, and Plasma Spray Physical Vapor Deposition (PS-PVD) will be particularly discussed. The testing results and demonstrations of advanced EBCs-CMCs in complex simulated engine thermal gradient cyclic fatigue, oxidizing-steam and CMAS environments will help provide insights into the coating development strategies to meet long-term engine component durability goals.

Processing and Properties↗

User's manual for rocket combustor interactive design (ROCCID) and analysis computer program. Volume 1: User's manual

The user's manual for the rocket combustor interactive design (ROCCID) computer program is presented. The program, written in Fortran 77, provides a standardized methodology using state of the art codes and procedures for the analysis of a liquid rocket engine combustor's steady state combustion performance and combustion stability. The ROCCID is currently capable of analyzing mixed element injector patterns containing impinging like doublet or unlike triplet, showerhead, shear coaxial, and swirl coaxial elements as long as only one element type exists in each injector core, baffle, or barrier zone. Real propellant properties of oxygen, hydrogen, methane, propane, and RP-1 are included in ROCCID. The properties of other propellants can easily be added. The analysis model in ROCCID can account for the influence of acoustic cavities, helmholtz resonators, and radial thrust chamber baffles on combustion stability. ROCCID also contains the logic to interactively create a combustor design which meets input performance and stability goals. A preliminary design results from the application of historical correlations to the input design requirements. The steady state performance and combustion stability of this design is evaluated using the analysis models, and ROCCID guides the user as to the design changes required to satisfy the user's performance and stability goals, including the design of stability aids. Output from ROCCID includes a formatted input file for the standardized JANNAF engine performance prediction procedure.

Muss, J. A.↗

User's manual for rocket combustor interactive design (ROCCID) and analysis computer program. Volume 2: Appendixes A-K

The appendices A-K to the user's manual for the rocket combustor interactive design (ROCCID) computer program are presented. This includes installation instructions, flow charts, subroutine model documentation, and sample output files. The ROCCID program, written in Fortran 77, provides a standardized methodology using state of the art codes and procedures for the analysis of a liquid rocket engine combustor's steady state combustion performance and combustion stability. The ROCCID is currently capable of analyzing mixed element injector patterns containing impinging like doublet or unlike triplet, showerhead, shear coaxial and swirl coaxial elements as long as only one element type exists in each injector core, baffle, or barrier zone. Real propellant properties of oxygen, hydrogen, methane, propane, and RP-1 are included in ROCCID. The properties of other propellants can be easily added. The analysis models in ROCCID can account for the influences of acoustic cavities, helmholtz resonators, and radial thrust chamber baffles on combustion stability. ROCCID also contains the logic to interactively create a combustor design which meets input performance and stability goals. A preliminary design results from the application of historical correlations to the input design requirements. The steady state performance and combustion stability of this design is evaluated using the analysis models, and ROCCID guides the user as to the design changes required to satisfy the user's performance and stability goals, including the design of stability aids. Output from ROCCID includes a formatted input file for the standardized JANNAF engine performance prediction procedure.

Muss, J. A.↗

Investigation of ZnSe-coated silicon substrates for GaAs solar cells

Studies are being carried out to determine the feasibility of using ZnSe as a buffer layer for GaAs solar cells grown on silicon. This study was motivated by reports in the literature indicating ZnSe films had been grown by metallorganic chemical vapor deposition (MOCVD) onto silicon with EPD values of 2 x 10(exp 5) cm(sup -2), even though the lattice mismatch between silicon and ZnSe is 4.16 percent. These results combined with the fact that ZnSe and GaAs are lattice matched to within 0.24 percent suggest that the prospects for growing high efficiency GaAs solar cells onto ZnSe-coated silicon are very good. Work to date has emphasized development of procedures for MOCVD growth of (100) ZnSe onto (100) silicon wafers, and subsequent growth of GaAs films on ZnSe/Si substrates. In order to grow high quality single crystal GaAs with a (100) orientation, which is desirable for solar cells, one must grow single crystal (100) ZnSe onto silicon substrates. A process for growth of (100) ZnSe was developed involving a two-step growth procedure at 450 C. Single crystal, (100) GaAs films were grown onto the (100) ZnSe/Si substrates at 610 C that are adherent and specular. Minority carrier diffusion lengths for the GaAs films grown on ZnSe/Si substrates were determined from photoresponse properties of Al/GaAs Schottky barriers. Diffusion lengths for n-type GaAs films are currently on the order of 0.3 microns compared to 2.0 microns for films grown simultaneously by homoepitaxy.

Huber, Daniel A.↗

Elevated Temperature Testing and Modeling of Advanced Toughened Ceramic Materials

The purpose of this report is to provide a final report for the period of 12/1/03 through 11/30/04 for NASA Cooperative Agreement NCC3-776, entitled "Elevated Temperature Testing and Modeling of Advanced Toughened Ceramic Materials." During this final period, major efforts were focused on both the determination of mechanical properties of advanced ceramic materials and the development of mechanical test methodologies under several different programs of the NASA-Glenn. The important research activities made during this period are: 1. Mechanical properties evaluation of two gas-turbine grade silicon nitrides. 2) Mechanical testing for fuel-cell seal materials. 3) Mechanical properties evaluation of thermal barrier coatings and CFCCs and 4) Foreign object damage (FOD) testing.

Keith, Theo G.↗

Thermochemistry of Protective Coatings and Molten Silicate Debris

The durability of gas-turbine engine components can be significantly affected by the ingestion of siliceous particles, which can melt at high temperature and corrode protective coatings that are essential for long life requirements. The silicate debris consists mainly of CaO-MgO-Al2O3-SiO2 (CMAS) and is usually ingested by aircraft engines during and after take-off, sticking to their hot surfaces and resulting in the formation of calcium rare-earth silicate oxyapatites. The thermochemistry of coatings and their reaction products with molten silicate debris are crucial to understand in order to improve the durability of gas-turbine engines. Here we discuss results of high temperature drop solution calorimetry, drop-and-catch calorimetry (DnC) and differential thermal analysis (DTA) techniques for the thermodynamic properties of both thermal barrier coatings (TBCs) and environmental barrier coatings (EBCs) and their reaction with CMAS compositions. The enthalpies of solution of Y2Si2O7, Yb2Si2O7, 31YSZ, and 16RESZ based coatings and the oxyapatite are moderately positive. However, oxyapatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb2Si2O7 and CaYb4Si3O13 than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. We also report for the first time the calorimetric measurements of the enthalpies of formation of rare-earth silicate based EBC coatings and oxyapatites (rare-earth, RE = Y, Yb, Gd, Dy, Er, Nd and Sm).

Costa, Gustavo↗

Behavior of the Si/SiO2 interface observed by Fowler-Nordheim tunneling

Thin-oxide (40-50 A) metal oxide semiconductor (MOS) structures are shown to exhibit, before large levels of electron tunnel injection, the near-ideal behavior predicted for a uniform trapezoidal barrier with thick-oxide properties. The oscillatory field dependence caused by electron-wave interference at the Si/SiO2 interface suggests an abrupt, one-monolayer barrier transition (approximately 2.5 A) consistent with earlier work. After tunnel injection of 10 to the 17th - 5 x 10 to the 18th electrons/sq cm, the barrier undergoes appreciable degradation, leading to enhanced tunneling conductance. Reproducible behavior is observed among different samples. This effect is found to be consistent with the generation of positive states in the region of the oxide near the Si/SiO2 interface (less than 20 A), where the tunneling electrons emerge into the oxide conduction band.

Maserjian, J.↗

High-Operating-Temperature Barrier Infrared Detector with Tailorable Cutoff Wavelength

A mid-wavelength infrared (MWIR) barrier photodetector is capable of operating at higher temperature than the prevailing MWIR detectors based on InSb. The standard high-operating-temperature barrier infrared detector (HOT-BIRD) is made with an InAsSb infrared absorber that is lattice-matched to a GaSb substrate, and has a cutoff wavelength of approximately 4 microns. To increase the versatility and utility of the HOT-BIRD, it is implemented with IR absorber materials with customizable cutoff wavelengths. The HOT-BIRD can be built with the quaternary alloy GaInAsSb as the absorber, GaAlSbAs as the barrier, on a lattice-matching GaSb substrate. The cutoff wavelength of the GaInAsSb can be tailored by adjusting the alloy composition. To build a HOT-BIRD requires a matching pair of absorber and barrier materials with the following properties: (1) their valence band edges must be approximately the same to allow unimpeded hole flow, while their conduction band edges should have a large difference to form an electron barrier; and (2) the absorber and the barrier must be respectively lattice-matched and closely lattice-matched to the substrate to ensure high material quality and low defect density. To make a HOT-BIRD with cutoff wavelength shorter than 4 microns, a GaInAsSb quaternary alloy was used as the absorber, and a matching GaAlSbAs quaternary alloy as the barrier. By changing the alloy composition, the band gap of the quaternary alloy absorber can be continuously adjusted with cutoff wavelength ranging from 4 microns down to the short wavelength infrared (SWIR). By carefully choosing the alloy composition of the barrier, a HOT-BIRD structure can be formed. With this method, a HOT-BIRD can be made with continuously tailorable cutoff wavelengths from 4 microns down to the SWIR. The HOT-BIRD detector technology is suitable for making very-large-format MWIR/SWIR focal plane arrays that can be operated by passive cooling from low Earth orbit. High-operating temperature infrared with reduced cooling requirement would benefit space missions in reduction of size, weight, and power, and an increase in mission lifetime.

Ting, David Z.↗

Investigation of the Mechanical Performance of Compliant Thermal Barriers

Compliant thermal barriers play a pivotal role in the thermal protection systems of advanced aerospace vehicles. Both the thermal properties and mechanical performance of these barriers are critical in determining their successful implementation. Due to the custom nature of many thermal barriers, designers of advanced spacecraft have little guidance as to the design, selection, and implementation of these elements. As part of an effort to develop a more fundamental understanding of the interrelationship between thermal barrier design and performance, mechanical testing of thermal barriers was conducted. Two different types of thermal barriers with several core insulation density levels ranging from 62 to 141 kg/cu m were investigated. Room-temperature compression tests were conducted on samples to determine load performance and assess thermal barrier resiliency. Results showed that the loading behavior of these thermal barriers was similar to other porous, low-density, compliant materials, such as elastomeric foams. Additionally, the insulation density level had a significant non-linear impact on the stiffness and peak loads of the thermal barriers. In contrast, neither the thermal barrier type nor the level of insulation density significantly influenced the room-temperature resiliency of the samples.

DeMange, Jeffrey J.↗

Thermal Residual Stress in Environmental Barrier Coated Silicon Nitride - Modeled

When exposed to combustion environments containing moisture both un-reinforced and fiber reinforced silicon based ceramic materials tend to undergo surface recession. To avoid surface recession environmental barrier coating systems are required. However, due to differences in the elastic and thermal properties of the substrate and the environmental barrier coating, thermal residual stresses can be generated in the coated substrate. Depending on their magnitude and nature thermal residual stresses can have significant influence on the strength and fracture behavior of coated substrates. To determine the maximum residual stresses developed during deposition of the coatings, a finite element model (FEM) was developed. Using this model, the thermal residual stresses were predicted in silicon nitride substrates coated with three environmental coating systems namely barium strontium aluminum silicate (BSAS), rare earth mono silicate (REMS) and earth mono di-silicate (REDS). A parametric study was also conducted to determine the influence of coating layer thickness and material parameters on thermal residual stress. Results indicate that z-direction stresses in all three systems are small and negligible, but maximum in-plane stresses can be significant depending on the composition of the constituent layer and the distance from the substrate. The BSAS and REDS systems show much lower thermal residual stresses than REMS system. Parametric analysis indicates that in each system, the thermal residual stresses can be decreased with decreasing the modulus and thickness of the coating.

Ali, Abdul-Aziz↗

In(x)Ga(1-x)As/GaAs Quantum-Well Infrared Photodetectors

Choice of materials for present quantum-well infrared photodetectors (QWIPs) affected principally by two considerations. One was that in comparison with GaAs, In(x)Ga(1-x)As is potentially superior quantum-well material because of its stronger absorption of infrared radiation. Other consideration was that in comparison with Al(x)Ga(1-x)As, which is usual barrier material in older devices, GaAs potentially superior barrier material because it exhibits superior transport properties (lower scattering and higher mobility of charge carriers). GaAs is well material in older devices and barrier material in present devices.

Gunapala, Sarath D.↗

Plasma observations of the solar wind interaction with Mars

Measurements with the plasma analyzers on the Mars-2, 3 and 5 spacecraft show that Mars deflects a large fraction of the incoming solar wind flow to form a strong bow shock. The bow shock is about 1.41 Rm from the center of the planet at the subsolar point and about 2.40 Rm at the terminator. These distances are similar to those for Venus at times of moderate solar activity. The inferred effective obstacle altitude is about 400-700 km. An ion cushion has been found which is similar in its properties to the Venus magnetic barrier. The formation of this cushion appears to cause the deflection of the solar wind. Inside the cushion but well above the ionosphere is found a region where the ions are at the background, the electrons are cool and the magnetic pressure dominates. This region may resemble a planetary magnetosphere.

Vaisberg, O. L.↗

An Ensemble Neural Network Model for Predicting Rare-Earth Oxide and Silicate Heat Capacities at High Temperature

In this work, a neural network model was developed to predict the constant pressure heat capacity for materials in the rare-earth oxide—silica material space. Several model architectures were trained and tested on heat capacity data generated from first-principles density functional theory calculations. Hyperparameter optimization was performed, and the optimal model was selected for heat capacity predictions. The optimal model architecture was found to have a root-mean-squared error of 5.12 ± 3.37 J/mol-K. The optimal model architecture was then used in a bagging ensemble model trained using the leave-one-group-out method to provide error estimates for model predictions. The out-of-bag score for the ensemble model was 0.997. The predicted heat capacities agree well with the DFT and experimental results and were computed orders of magnitude faster than DFT simulations. Machine learning shows the potential to provide a suitable surrogate model for thermochemical property predictions for candidate environmental barrier coating materials but refining of input material features and model architectures could further improve accuracy for these models.

environmental barrier coatings↗

Investigation of Thermal High Cycle and Low Cycle Fatigue Mechanisms of Thick Thermal Barrier Coatings

Ceramic thermal barrier coatings have attracted increased attention for diesel engine applications. The advantages of using the ceramic coatings include a potential increase in efficiency and power density and a decrease in maintenance cost. Zirconia-based ceramics are the most important coating materials for such applications because of their low thermal conductivity, relatively high thermal expansivity and excellent mechanical properties. However, durability of thick thermal barrier coatings (TBCS) under severe temperature cycling encountered in engine conditions, remains a major question. The thermal transients associated with the start/stop and no-load/full-load engine cycle, and with the in-cylinder combustion process, generate thermal low cycle fatigue (LCF) and thermal high cycle fatigue (HCF) in the coating system. Therefore, the failure mechanisms of thick TBCs are expected to be quite different from those of thin TBCs under these temperature transients. The coating failure is related not only to thermal expansion mismatch and oxidation of the bond coats and substrates, but also to the steep thermal stress gradients induced in the coating systems. Although it has been reported that stresses generated by thermal transients can initiate surface and interface cracks in a coating system, the mechanisms of the crack propagation and of coating failure under the complex LCF and HCF conditions are still not understood. In this paper, the thermal fatigue behavior of an yttria partially stabilized zirconia coating system under simulated LCF and HCF engine conditions is investigated. The effects of LCF and HCF on surface crack initiation and propagation are also discussed.

Zhu, Dong-Ming↗

Development and Property Evaluation of Selected HfO2-Silicon and Rare Earth-Silicon Based Bond Coats and Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

Ceramic environmental barrier coatings (EBC) and SiC/SiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiC/SiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si and rare earth Si based EBC bond coat EBC systems for SiC/SiC CMC combustor and turbine airfoil applications are investigated. High temperature properties of the advanced EBC systems, including the strength, fracture toughness, creep and oxidation resistance have been studied and summarized. The advanced NASA EBC systems showed some promise to achieve 1500C temperature capability, helping enable next generation turbine engines with significantly improved engine component temperature capability and durability.

Oxidation and cyclic durability↗

Dual ion beam processed diamondlike films for industrial applications

Single and dual beam ion source systems are used to generate amorphous diamondlike carbon (DLC) films, which were evaluated for a variety of applications including protective coatings on transmitting materials, power electronics as insulated gates and corrosion resistant barriers. A list of the desirable properties of DLC films along with potential applications are presented.

Mirtich, M. J.↗

Acoustic Issues in Human Spaceflight

NASA is concerned about acute effect of sound on crew performance on International Space Station (ISS), and is developing strategies to assess and reduce acute, chronic, and delayed effects of sound. High noise levels can cause headaches, irritation, fatigue, impaired sleep, headache, and tinnitus and have resulted in an inability to hear alarms. Speech intelligibility may be more impaired for crew understanding non-native language in a noisy environment. No hearing loss occurred, but significant effects on crew performance and communication occurred. Permanent Threshold Shifts (PTS) have not been observed in the US shuttle program. Russian specification for noise in spacecraft is 60 dBA (awake) and 50 dBA (asleep) while the U.S. noise specification on ISS is NC 50 (awake) and NC 40 (asleep) with a 85 dBA hazard limit. Background noise levels of ISS modules have measured 56-69 dBA. Treadmill exercise operations measure 77 dBA. Alarms are required to be 20 dBA above ambient. Hearing protection is recommended when noise exceeds 60 dB 24 hour Leq. Countermeasures include hearing protection and design/ engineering controls. Advanced composite materials with excellent low frequency attenuation properties could be applied as a barrier protection around noisy equipment, or used on personal protective equipment worn by the crew. Hearing protection countermeasures include foam ear inserts, passive muff headsets, and active noise reduction headsets. Oto-acoustic emissions (OAE) could be used to monitor effectiveness of hearing protection countermeasures and tailor hearing protection countermeasures to individual crewmembers. Micro-gravity, vibration, toxic fumes, air quality/composition, stress, temperature, physical exertion or some combination of the above factors may have interacted with moderate long-term noise exposure to cause significant hearing loss. Longitudinal studies will need to address what co-morbidity factors, such as radiation, toxicology, microgravity effects (fluid shift), aging, are involved with hearing loss.

Clark, Jonathan B.↗